KR0143779B1 - Long chain aliphatic hydrocarbyl amine additive having an oxy-alkylene hydroxy linking group - Google Patents

Abstract

Long chain aliphatic hydrocarbyl amine additives which comprise a long chain aliphatic hydrocarbyl component, an amine component and an oxy-alkylene hydroxy connecting group connecting the aliphatic hydrocarbyl component and amine component are useful as deposit control additives in fuel compositions and as dispersants in lubricating oil compositions.

Description

[Title of the Invention]

Long chain aliphatic hydrocarbyl amine additive having an oxy-alkylene hydroxy linking group

BACKGROUND OF THE INVENTION [

[0001]

Many of the precipitate-forming materials are inherent in the hydrocarbon fuel. When used in an internal combustion engine, these materials tend to form deposits around and around the stenotic zone of the engine that is contacted by the fuel. Typical, sometimes violently loaded typical areas due to the formation of the deposits include a carburetor outlet, throttle and venturi, and engine suction valve.

The sediments adversely affect the operation of the vehicle. For example, carburetor throttles and deposits from Venturi increase the amount of unburned hydrocarbons and carbon monoxide emitted from the combustion chambers by increasing the ratio of fuel to air in the gas mixture in the combustion chamber. The high fuel-air ratio also reduces the distance traveled by the vehicle from the vehicle. In other words, when the precipitation becomes too heavy, the precipitation by the engine aspiration valve limits the flow of the gas mixture into the combustion chamber. This restriction weakens the engine of air and fuel and causes the engine to lose power. Bulb deposits also increase the likelihood of failure of the valve due to combustion and improper valve position. In addition, these deposits can break down and enter the combustion chamber, which can cause mechanical damage to the piston, piston rings, engine heads, and the like.

Formation of these precipitates may be inhibited as well as inhibited by mixing the active detergent in the fuel. These detergents improve the engine's function and longevity by functioning to clean areas where harmful deposits are likely to settle. Depending on the degree, there are many detergent-type gasoline additives that are currently available and that perform these functions.

Two factors complicate the use of such detergent-type gasoline additives. First, with regard to automotive engines, which require the use of unleaded gasoline (to prevent disabling of the catalytic converter used to reduce emissions), the use of high octane to prevent knocking and simultaneous damage when it occurs I found it difficult to provide gasoline. The main problem lies in the extent of the increase in octane requirement due to sediment formed by commercial gasoline, where the octane requirement increase (ORI).

The basic ORI problem is as follows. If each engine is new, it needs some minimum octane fuel to operate satisfactorily without pinging and / or knocking. When operating the engine with some gasoline, this minimum octane number increases, and in most cases, when the engine is operated on the same fuel for an extended period of time, it will be in parallel. This is obviously due to the amount of sedimentation in the combustion chamber. Typically, after reaching 5,000 to 15,000 miles of automobiles, parallelism is reached.

The specified increase in octane rating for a particular engine using commercial gasoline will vary from 5 to 6 octane units in parallel to 12 units or 15 units, depending on the gasoline composition, engine design and mode of operation. So the seriousness of the problem appears. In the case of a new car, a typical octane rule of 85 cars may require 97 octane gasoline for proper operation in months and may require almost unleaded gasoline that can generate octane. The ORI problem also exists to some extent in engines that run on leaded fuel. U.S. Patent 3,144,311; 3,146,203; And 4,247,301 disclose lead-containing fuel compositions that reduce ORI problems.

The ORI problem is solved by the fact that the most common way to increase the octane content of unleaded gasoline is to increase its aromatics. However, this eventually leads to the need for large octane. Moreover, some of the currently used nitrogen-containing compounds used as sediment-inhibiting mineral oils or polymeric carriers may also significantly affect the ORI of engines using unleaded fuel.

It is therefore particularly desirable to provide a precipitate inhibiting additive that effectively inhibits the precipitation in the intake system of the engine without consequently affecting the problem.

In this regard, hydrocarbyl poly (oxyalkylene) aminocarbamates are commercially successful fuel additions that minimize the ORI by inhibiting the deposits in the combustion chamber.

A second complicated factor relates to the lubricant compatibility of the fuel additive. Due to their higher boiling point than the gasoline itself, the fuel composition tends to accumulate on the surface of the combustion chamber of the engine. The accumulation of this additive eventually leads to the lubricant in the engine crankcase through the blow-by process and / or through the cylindrical wall and piston ring wipe-down. In some cases, as much as 25% -30% of the non-volatile fuel component, including the fuel additive, will eventually accumulate in the lubricant. Such a fuel additive may accumulate enough lubricant during this interval, since the recommended runoff for any engine may be as high as 7500 miles or more. If the fuel addition can not be sufficiently mixed with the lubricating oil, the accumulation of such an oil-incompatible fuel additive can actually affect the precipitate in the crankcase as measured by the continuous (Sequen V-D) test.

Despite the fact that some fuel additives are also known to be lubricating oil dispersants, they increase the solubility of certain fuel additives in lubricating oils, i.e. oils containing some other additives.

There are several theories about the causes of lubricant oil incompatibility of certain fuel additives.

Some of the fuel additives when found in lubricating oils without being bound by any theory are hampered by another additive contained in the lubricating oil and are in equilibrium with the efficacy of these additives, Or more of these additives may be dissolved. In either case, the reciprocity of the fuel additive with another additive in the lubricating oil is proved to be lower than the desired crankcase precipitation itself, as measured by continuous V-D engine testing.

In another theory, the accumulation of fuel additive in the lubricant during the outflow pause may be higher than its maximum solubility in the lubricant. In this theory, these excess fuel additives are insoluble in the lubricating oil and are caused by increased crankshaft precipitation.

Another theory is that the fuel additive is decomposed in the lubricating oil during engine operation and that the degradation products are attributed to increased crankcase precipitation.

In some cases, the non-fuels additive with the lubricating oil is less desirable because it will increase the sediment in the crankcase when used during engine operation. This problem can be serious. For example, hydrocarbyl poly (oxyalkylene) aminocarbamate fuel additives, including hydrocarbyl poly (oxybutylene) aminocarbamates, are known to have dispersibility in lubricating oils. In this respect, due to the poly (oxyalkylene group), the hydrocarbyl poly (oxyalkylene) aminocarbamate can be synthesized from a hydrocarbyl polyaminocarbamate without poly (oxyalkylene) group and another carbamylamine composition It is recognized that the cost for the service is substantially higher. It is therefore particularly advantageous to develop their compositions due to their low cost of manufacture and their chemical similarity to hydrocarbon-based lubricants and lubricant additives.

The present invention relates to a novel class of dispersant additives wherein the fuel additive minimizes ORI by inhibiting combustion chamber precipitation and lubricant additives are compatible with lubricant compositions. These additives are also useful as dispersants in lubricating oil compositions themselves. The novel additive of the present invention is a long chain aliphatic hydrocarbyl amine composition having an epihalohydrin-derived linking group linking a long chain aliphatic hydrocarbyl component and an amine component.

A polyoxyalkylene carbamate containing a polyoxyalkylene chain attached to the hydroxy-hydrocarbyloxy-terminated oxyalkylene unit of 2 to 5 carbon atoms bonded to the nitrogen atom of the polyamine through an oxy carbonyl group It has been known to be a sedimentation inhibiting additive useful in fuel compositions. See, for example, U.S. Patent Nos. 4,160,648; 4,191,537; 4,236,020; And 4,288,612.

Hydroxycarbyl poly (oxyalkylene) polyamines are also known to be useful as dispersants in lubricating oil compositions. See, for example, U.S. Patent No. 4,247,301.

The use of certain polyoxyalkyleneamines in diesel fuel to improve the operation of injector-equipped engines is known. See, for example, U.S. Patent No. 4,568,358.

A polyoxyalkylene prepared by reacting a polyoxyalkylene glycol monoether and a halogen-containing polyoxyalkylene glycol resulting from the reaction of a hydroxyl-containing compound having 1 to 8 hydroxyl groups with a halogen-containing compound with an amine Polyamines are known as fuel cleaning additives. See, for example, U.S. Patent No. 4,261,704.

First, a polyalkylene intermediate of a polyoxyalkylene compound prepared by reacting a polyoxyalkylene polyol having 1 to 8 hydrogenated sites with epihalohydrides and then reacting the resulting polyether with an amine And crosslinking agents for synthetic resins. See, for example, U.S. Patent No. 4,281,199.

SUMMARY OF THE INVENTION [

The present invention relates to a new class of long chain aliphatic hydrocarbyl amine additives comprising an long chain aliphatic hydrocarbyl component, an amine component, and an oxy-alkylene hydroxy linking group linking the aliphatic hydrocarbyl component and the amine component Wherein the linking group has two oxygen atoms, a linking oxygen atom and a hydroxyl oxygen and the linking oxygen atom in the linking group is covalently bonded to the carbon atom in the aliphatic hydrocarbyl component and the remaining carbon atoms of the linking group. The long chain aliphatic hydrocarbyl component is high molecular weight and long enough chain length to allow the resulting additive to be soluble in liquid hydrocarbons, including boiling fuels, in gasoline or diesel ranges and compatible with lubricating oils.

These additives have beneficial dispersibility when used in fuel compositions. In addition, unlike additives containing hydrocarbyl components directly linked to amine components, the use of these additives in lead-free fuels does not cause the problems discussed above by combustion chamber precipitation and continuous ORI. Additives with aliphatic hydrocarbyl components directly connected to amine components when used as fuel additives in lead-free fuels are known to cause significant precipitation formation and continuous ORI.

In addition, the present invention relates to a fuel composition comprising gasoline and boiling hydrocarbons in the diesel range and from about 30 to about 5000 ppm of an aliphatic hydrocarbyl additive of the present invention.

The present invention also relates to a fuel concentrate consisting of an aliphatic hydrocarbyl additive of the present invention and from about 5 to about 50 weight percent of a stable oleophilic organic solvent boiling in the range of 65.5 DEG C to 204.5 DEG C.

The additives of the present invention are also useful as dispersants and / or detergents in lubricating oil compositions. The present invention therefore also relates to a lubricating oil composition comprising an amount of lubricating viscosity oil and an amount of additive sufficient to impart dispersibility and / or cleanliness. The additive of the present invention may also be formulated as a lubricant concentrate consisting of about 90 to about 50 weight percent of a lubricating viscosity oil and about 10 to about 50 weight percent of the inventive additive.

DETAILED DESCRIPTION OF THE INVENTION [

The long chain aliphatic hydrocarbyl amine additive of the present invention comprises a long chain aliphatic hydrocarbyl component and an amine component linked by an epihalohydrin-derivatizing linkage group through a linking oxygen. The linking group may be liberated from the aliphatic hydrocarbyl component by the heat so that the remaining hydrocarbyl portion is oxidatively decomposed by heat in the combustion chamber to form a harmful precipitate.

[Preferred long-chain aliphatic hydrocarbyl component]

The long chain aliphatic hydrocarbyl component is long enough to allow the resulting additive to be boiling in the gasoline or diesel range and becoming soluble in liquid hydrocarbons containing fuel compatible with the lubricating oil.

The hydrocarbyl component may be an aliphatic or aliphatic hydrocarbyl group and there will be no aromatic unsaturation, except for the accidental amount of aromatic structure that may be present in petroleum mineral oil. The hydrocarbyl group is derived from petroleum mineral oils or polyolefins (homopolymers or higher polymers of 1 to 6 carbon atoms) and ethylene is polymerized with higher homologs. The olefins may be mono-unsaturated or poly-unsaturated, but the polyunsaturated allphenes require that the final product be reduced to remove all residual unsaturated moieties, except for one olefin moiety.

A preferred source for obtaining high molecular weight hydrocarbons from petroleum mineral oils is naphthenic-transparent raw materials. For the polyolefins, preferred polymers are polypropylene, polyisobutylene, poly-1-butene, copolymers of ethylene and isobutyl, copolymers of propylene and isobutylene, poly-1-pentene, 1-pentene, poly-1-hexene, poly-3-methylbutene-1, polyisoprene and the like.

The long chain aliphatic hydrocarbyl component will normally have at least one branch per six carbon atoms along the chain, preferably having at least one chain per four carbon atoms along the chain, particularly preferably along the chain There will be about one branch per two carbon atoms. These branched chain hydrocarbon groups are readily prepared by polymerization of olefins of from 3 to 6 carbon atoms, preferably from 3 to 4 carbon atoms, more preferably propylene or isobutylene. The additional polymerizable olefin employed is normally -1 olefin. The bridges have from 1 to 4 carbon atoms, more usually from 1 to 2 carbon atoms, preferably methyl.

The long chain aliphatic hydrocarbyl component has a high molecular weight sufficient to maintain new tack in the carburetor, in the fuel injector and in the intake valve; Typically, long chain aliphatic hydrocarbyl moieties are long chains in order of 50 carbon atoms, or have a larger carbon number arrangement for sufficient cleaning power.

Preferred long chain aliphatic hydrocarbyl components are derived from high molecular weight olefins or alcohols. It is also possible to use polymeric hydrocarbons or high molecular weight alcohols prepared from olefins corresponding thereto. ;

Polymeric hydrocarbons or olefins used to prepare corresponding alcohols have an average molecular weight of about 500 to about 5000.

Preferred are polymeric hydrocarbons having an average molecular weight of about 700 to about 3000, more preferably from about 900 to about 2000, and particularly preferably from about 950 to about 1600.

Preferred polymeric hydrocarbons used to make the alcohols include polypropylene, polyisopropylene, polybutylene, polybutylene and polyisobutylene. Preferred are those of polymerized hydrocarbons having at least 50 carbons.

Particularly preferred are long-acting, fat-derived hydrocarbyl components derived from polyisobutene containing reactive polyisobutene, i. E. At least about 50% more reactive methylvinylidene isomers. Suitable polyisobutenes include those prepared using BF ₃ catalysts. The preparation of such polyisobutene is described in U.S. Patent No. 4,605,808. Such reactive polyisobutenes react to give high molecular weight alcohols in which the hydroxyl is at the end of the hydrocarbon chain (close to).

The preferred long-chain aliphatic hydrocarbyl components in the additives of the present invention are conveniently prepared from alcohols which can be prepared from the corresponding olefins through conventional processes. Such a process involves hydration of the double bond to obtain the alcohol.

Suitable processes for preparing such long chain alcohols are described in the literature (e.g., by H. C. Brown, Boran, Organic Synthesis, John Wiley and his Son (1975); A. T. Harrison and S. Harrison, Organic An overview of synthetic methods, Willie-InterScience, New York (1971), 119-122); This is illustrated in the examples of negligence.

(Preferred amine component)

The amine component of the long chain aliphatic hydrocarbyl amine additives of the present invention is preferably derived from a polyamine having 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. The polyamines are preferably reacted with an intermediate having an amine reactive site in order to obtain a long chain aliphatic hydrocarbyl amine additive which can be used within the scope of the present invention. The intermediates themselves are derived from long chain aliphatic hydrocarbyl alcohols by reaction with epichlorohydrin. Polyamines, including diamines, on average give the product at least about one basic nitrogen atom per product molecule, i.e., a nitrogen atom that can titrate to a strong acid. The polyamines preferably have a carbon-to-nitrogen ratio of about 1: 1 to about 10: 1.

(A) hydrogen, (B) a hydrocarbyl group of 1 to 10 carbon atoms, (C) an acyl group of 2 to about 10 carbons and (D) a monoceno, monohydroxy, mononitro, monocyano , Lower alkyl and lower alkoxy derivatives of (b) and (c). Lower alkyl as used in such terms as lower alkyl or lower alkoxy means a group containing from one to about six carbon atoms. At least one of the substituents on one of the basic nitrogen atoms of the polyamine is hydrogen. For example, at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom.

Means an organic group consisting of hydrocarbyl aliphatic, substituted, aromatic or mixtures thereof, such as carbon and hydrogen which may be aralkyl, as used to describe the amine component of the present invention. Preferably, the hydrocarbyl group is relatively aliphatic unsaturation, i.e. there is no unsaturation of ethylene and acetylene, especially acetylene. The substituted polyamines of the present invention are N-substituted polyamines which are common, but not essential. Exemplary hydrocarbyl groups and substituted hydrocarbyl groups include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, and the like; Alkenyls such as propenyl, isobutenyl, hexenyl, octenyl and the like; Hydroxyalkyl such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxy-isopropyl, 4-hydroxybutyl and the like; Ketoalkyl such as 2-keto propyl, 6-ketooctyl and the like; (2-ethoxyethoxy) ethoxy, ethyl, propyl, isopropyl, butyl, isobutyl, 9,12-tetraoctatetradecyl, 2- (2-ethoxyethoxy) hexyl, and the like. Among the above-mentioned (C) substituents, the acyl group is such as propionyl, acetyl, and the like. More preferred substituents are hydrogen, C ₁ -C ₆ alkyl and C ₁ -C ₆ hydroxyalkyl.

In substituted polyamines, substituents are found in any atom capable of accepting them. The substituted atoms, such as substituted nitrogen atoms, are generally not geometrically equivalent, and thus the substituted amines that can be used in the present invention are polyamines that are monosubstituted with a substituent group located at an equivalent atom and / - < / RTI > substituted polyamines.

More preferred polyamines that can be used within the scope of the present invention are polyalkylene polyamines including alkylenediamines and substituted polyamines (e.g., alkyl and hydroxyalkyl substituted polyalkylene polyamines). Preferably, the alkylene group of the polyamine contains from 2 to 6 carbon atoms, preferably between 2 and 3 carbon atoms between the nitrogen atoms. Such alkylene groups include ethylene, 1,2-propylene, 2,2-dimethyl-propylene trimethylene, 1,3,2-hydroxypropylene and the like. Examples of such polyamines include ethylenediamine, diethylenetriamine, di (trimethylene) triamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and penta-ethylenehexamine do. Such amines include isomers such as polyamines of branched chains and polyamines substituted by hydroxy and hydrocarbyl with the aforementioned substituted polyamines. Of the polyalkylene polyamines, those containing from ₂ to 12 amine nitrogen atoms and from ₂ to 24 carbon atoms are particularly preferred and C ₂ -C ₃ alkylene polyamines are most preferred. Particularly preferred are lower polyalkylene polyamines such as ethyleneamine, diethylenetriamine, propylenediamine, dipropylenetriamine and the like. Particularly preferred are ethylenediamine and diethylenetriamine.

Amine components in the additives of the present invention can also be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds. Wherein the heterocycle is comprised of one or more rings of 5-6 members containing oxygen and / or nitrogen. The heterocycles may be saturated or unfused and may be substituted with groups selected from (A), (B), (C) and (D) mentioned above. The heterocycles include, for example, 2-methylpiperazine, N- (2-hydroxyethyl) piperazine, 1,2-bis- (N-piperazinyl) (3-aminoethyl) -3-pyrrolidine, 3-aminopyridine, 2-aminopyridine, 2- Pyrrolidine, N- (3-aminopropyl) -morpholine, and the like. Among the heterocyclic compounds, piperazine is preferable.

Another class of suitable polyamines from which amine components can be derived are the diaminoethers of the formula IX.

H ₂ NX ₁ (OS ₂ ) rNH ₂ (IX)

Wherein X ₁ and X ₂ are independently an alkylene of from 2 to about 5 carbon atoms and r is an integer from 1 to about 10. The diamines of the general formula IX are disclosed in U.S. Patent No. 4,521,610, which is hereby incorporated by reference for the purpose of announcing such diamines.

Typical polyamines that can be used to make the compounds of the invention by reacting with the intermediates include the following. (Ethylene diamine), ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, dimethylaminopropylene diamine, N- Amino-N-ethylpiperidine, N- (beta-aminoethyl) morpholine, N, N'-di (beta-aminoethyl) Piperazine, N, N'-di (beta-aminoethylimidazolidin-2; N (beta-cyanoethyl) ethane- 1,2-diamine, 1-amino-3,6,9-triazaocta (N-acetyl-N'-methyl-N- (beta-amino-ethyl) -hexanoic acid, N- (beta-aminoethyl) hexahydrotriazine, N- (beta-aminoethyl) hexahydrotriazine, N-acetyl-1,2-propane- Beta-aminoethyl) -1,3,5-dioxazine, 2- (2-amino-ethylamino) -ethanol, 2- [2- -Ethylamino) ethylamino] -ethanol. ≪ / RTI >

In many cases, the polyamines used as reactants in the production of the additives of the present invention are not single compounds but mixtures of one or several compounds in excess of the indicated average composition. For example, tetraethylenepentamine prepared by polymerization of aziridine or by the reaction of dichloroethyl and ammonia has lower and higher amine elements such as triethylenetetramine, substituted piperazine and pentaethylenesamine, Tetraethylenepentamine, and empirical formulas of the total amine composition approach the tetraethylenepentamine closely. Finally, when the various nitrogen atoms of the polyene are not geometrically uniform, some substitutional isomers in the preparation of the inventive cargo are likely and are included in the final product. Amines, isocyanates and their reactions are described in Organic Chemistry of Nitrogen in Cigelwix, Clarendon Press, Oxford, 1966; Organic Compound Chemistry of Noller, Chem. Souders, Philadelphia, 2nd Edition, 1957, and Kirk-Otmer Chemistry, 2nd Edition, especially Vol. 2, pp. 99-116.

(Connection group)

The linking group connecting the long chain aliphatic hydrocarbyl component and the amine component is a double group wherein the ether linkage oxygen may be considered to be the terminal hydroxyl oxygen of a long chain alcohol leading to a long chain aliphatic hydrocarbyl component, The remainder of the group is derived from epihalohydrin. It functions to link the two components so that the oxygen atom of the linking group is covalently bonded to the carbon atom of the long chain aliphatic hydrocarbyl component and the oxygen atom of the remainder of the linking group.

Epihalohydrin has the following structure.

Y is halogen.

In the reaction in which an alcohol is reacted with an epihalohydrin and then reacted with an amine to obtain an additive of the present invention, the epoxide ring is opened to form a hydroxyl-containing linkage ring. The ring-

- - or - ≪ / RTI > The mechanism of the reaction is - - It is believed that this is in large part in harmony with the group.

(A preferred long chain aliphatic hydrocarbyl amine additive)

Generalized preferred structural formulas for the long chain aliphatic amine additives of the present invention are as follows.

R - X - Am (I)

Wherein R is an aliphatic hydrocarbyl moiety containing at least about 50 carbon atoms, as set forth above; Am is an amine component as described above; X is a linking group wherein the linking oxygen may be considered to be the terminal hydroxyl oxygen of the long chain alcohol leading to the long chain aliphatic hydrocarbyl component and the remainder of the linking group is derived from the epihalohydrin. The linking group may have one of the following two different structures.

- - or -

- It is believed that the linking group structure occupies most of the mixture of product additives.

Preferred long-chain aliphatic hydrocarbyl amine additives employed in the present invention have at least one basic nitrogen atom per molecule. Basic nitrogen sources include, for example, amido nitrogen, i.e.,

Such as primary, secondary, or tertiary amino nitrogen, as distinguished from strong acid.

Preferably, the basic nitrogen is present as a primary or secondary amino group.

The preferred long-chain aliphatic amine additives of the present invention have an average molecular weight of from about 700 to about 3000, preferably from about 1000 to about 2000, and most preferably from about 1000 to about 1600.

A particularly preferred class of long chain aliphatic hydrocarbyl amine additives according to the present invention can be illustrated by the following. ;

Wherein R is a polyisobutenyl group having a chain length of at least 50 carbon atoms, R ₁ is an alkylene of 2 to about 6 carbon atoms, and p is an integer of 1 to about 6.

(Overall manufacturing)

The additives used in the present invention can be conveniently prepared by first reacting an aliphatic hydrocarbyl alcohol with an epihalohydrin to obtain an intermediate and then reacting it with an amine to obtain a desired aliphatic hydrocarbyl amine additive.

The preparation of the aliphatic hydrocarbyl alcohols is well known to those skilled in the art. For example, H. Seed. Brown, organic synthesis by borane, John Willy Anderson (1975).

The preparation of polyoxyalkylene polyamines for reacting halogenated ethers with polyamines is disclosed in U.S. Patent No. 4,261,704. This disclosure is incorporated herein by reference.

Thus, an aliphatic hydrocarbyl alcohol is reacted with an epihalohydrin to obtain an intermediate having a halo terminal group. The alkyl halide intermediate is then reacted with the polyamine to obtain the additive of the present invention.

The epihalohydrin used in the present invention corresponds to the following. :

In the transplantation, Y is halogen.

In practicing the present invention, the preferred epihalohydrin is either epichlorohydrin or epibromohydrin.

When an aliphatic hydrocarbyl alcohol is reacted with an epihalohydrin, a halohydrin ether intermediate is produced. In general, the reaction is carried out at a temperature of from about 30 ° C to about 100 ° C, preferably from about 50 ° C to about 80 ° C. This reaction is generally completed within about 0.5 to about 5 hours. Typical reaction times range from about 2 hours to about 4 hours. A solvent may be used; Examples of suitable solvents include those xylene, benzene, toluene, C ₉ aromatic solvents, naphthenic solvents and the like tenseong.

This reaction is carried out in the presence of a catalyst. Suitable catalysts include those of the Friedel-Craft type, such as AlCl ₃ , BF ₃ , ZnCl ₂ and FeCl _3, HF, H ₂ SO ₄ , H ₃ PO _4, and the like. A preferred catalyst is borofluoroboric acid which is conveniently developed in the form of an etal. Generally, from about 0.1 parts to about 5 parts of catalyst are used per 100 parts by weight of alcohol. Almost equal amounts of epihalohydrin and alcohol are used.

The reaction of the resulting halohydrin ether intermediate with the amine can be carried out purely or preferably in solution. Suitable solvents include organic solvents such as xylene, C ₉ aromatic solvents, naphthenic solvents and the like. The reaction is carried out at a temperature in the range of from about 0 ° C to 200 ° C, preferably in the range of from about 100 ° C to 150 ° C, and generally within about 4 hours to about 12 hours. The product is isolated by conventional processes such as washing and scripping under the protection of vacuum filtration and the like.

The molar ratio of amine to halohydrin ethyl intermediate is generally in the range of about 1 to about 5 moles of amine / halohydrin ether intermediate mole, and more typically in the range of about 2 to about 3 moles of amine per mole of intermediate . Large amounts of excess amines are used because they usually require the inhibition of poly-substitution of polyamines. In addition, preferred adducts are monoalkylamine compounds that are contrary to bis-alkylamines or unsubstituted aminoethers.

These reactions or reactions can be carried out with or without a reaction solvent. Reaction applications are generally used at any time to reduce the viscosity of the reactants and products and to minimize the formation of unwanted by-products. These solvents must be stable to reactants and reaction products and inert. Depending on the reaction temperature, the particular halohydrin ethyl intermediates used, the molar ratios as well as the degree of reactivity, the reaction time may vary from about 1 hour to about 24 hours.

After the reaction has been carried out for a sufficient period of time, the reaction mixture may be extracted with a hydrocarbon-water or hydrocarbon-alcohol-water medium to maintain the product from any low molecular weight amine salt and any unreacted polyamine that may be formed have. The product can then be separated by evaporation of the solvent. Further, purification by a conventional method such as column chromatography with silica gel may be effective.

(Fuel composition)

The long chain aliphatic hydrocarbyl amine additives of the present invention are generally used for hydrocarbon distillate fuels. The appropriate concentration of this additive required to fix the desired detergency and dispersibility depends on the presence of detergents, dispersants and other additives in the fuel used.

However, in general, from 30 to 5000 ppm by weight, preferably from 100 to 500 ppm, more preferably from 200 to 300 ppm, of long chain aliphatic hydrocarbyl amine additive per basic fuel portion is required to obtain the best results. Lesser amounts of long chain aliphatic hydrocarbyl amine additives may be used if other detergents are present. For use as a carburetor detergent alone, a low concentration of, for example, 30 to 70 ppm may be desirable. A high concentration, that is, 2000 to 5000 ppm, may have cleaning effect by fuel chamber precipitation.

The precipitation inhibiting additive may also be formulated as a concentrate using a stable, lipophilic organic solvent that boils in an inert solvent at a temperature ranging from about 65.5 DEG C to about 204.5 DEG C. Preferred are aliphatic or aromatic hydrocarbons, such as benzene, toluene, xylene, or high boiling aromatic or aromatic synergists. Mixtures of aliphatic alcohols of from about 3 to about 8 carbon atoms, such as isopropanol, iso-butylcarbinol, n-butanol and the like, with hydrocarbon solvents are also suitable for use with detergent-dispersants. The amount of additive in the concentrate is usually at least 5 percent by weight and generally does not exceed 50 percent by weight, preferably 10 to 30 percent by weight.

When using any of the long chain aliphatic hydrocarbyl amine additives of the present invention, especially those having at least one basic nitrogen, it is possible to add a demulsifier (emulsifier) to the gasoline or diesel fuel composition It may be desirable to add it. These releasing fire is generally added to the fuel composition at 1 to 15 ppm. Suitable Dimelinefires include, for example, phenol containing high molecular weight glycols available from Petrolite Corporation, St. Louis, Trilit Division, L-1562 And the OLOA 2503Z, available from Sébron Chemical Company, San Francisco, Calif. .

In gasoline fuels, another fuel additive may also be used, such as an antiknock agent, such as methylcyclopentylethyl manganese tricarbonyl, tetramethyl or tetraethyl lead, or other dispersants or various substituted succinic acid imides, amines, etc. Cleaning agents are included. Lead removers such as aryl halides such as dichlorobenzene or alkyl halides such as ethylene dibromide may also be included. In addition, there may be antioxidants, metal cheating agents, and dimers fire.

In diesel fuel, another well-known additive can be used such as pour point depressant, flow improver, cetane improvement braking.

(Lubricating oil composition)

The long chain aliphatic hydrocarbyl amine additives of the present invention are useful as dispersant additives in lubricating oil applications. As used herein the additive is usually present in the total composition in a weight of from 0.2 to 10 percent by weight, preferably from about 0.5 to 8 percent by weight, more preferably from about 1 to 6 percent by weight. The lubricating oil used in conjunction with the additives of the present invention may be mineral oil or a synthetic lubricating viscous and preferably suitable for use in the crankcase of an internal combustion engine of an internal combustion engine. The crankcase lubricant usually has a viscosity from 0 ° F to 1300 ° C to 210 ° F (99 ° C) to 22.7 ° C. The lubricants can be obtained synthetically or from natural resources. The mineral oil to be used as a base oil in the present invention mainly includes paraffin oil, naphthenic oil and other oils used in a lubricating oil composition. The synthetic oils include both synthetic hydrocarbon oils and synthetic esters. Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having suitable viscosities. Particularly useful are C ₆ to C ₁₂ alpha olefins such as 1-decane trimer and hydrogenated liquid oligomers. Similarly, alkylbenzenes of appropriate viscosity, such as didodecylbenzene, may be used. Useful synthetic esters include esters of monohydroxyalkanols and polyols, as well as alkoxylated and polycarboxylic acids. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilauryl sebacate and the like. May be used as complex esters prepared from mixtures of mono and dicarboxylic acids with mono and dihydroxyalkanols.

It is useful as a mixture of hydrocarbon oil and synthetic oil. For example, a mixture of 10-25 weight percent hydrogenated 1-decane trimer and 75-90 weight percent 150SUS (100 DEG F) mineral oil becomes a good lubricant base.

Lubricant concentrates are also included within the scope of the present invention. The concentrates of the present invention typically comprise about 90 to 50 weight percent of a lubricating viscous oil and about 10 to 50 weight percent of the present additive. Typically, the concentrates contain sufficient diluent to facilitate handling during transport and storage. Suitable diluents for the concentrate include any inert diluent, preferably a lubricating viscous oil, so that the concentrate can be easily mixed with the lubricating oil to make a lubricating oil composition. Suitable lubricating oils that can be used as diluents typically have a viscosity in the range of about 50 to about 500 Saybolt Universal Second (SUS) at 100 占 ((30 占 폚), even though lubricating viscous oil may be used.

Other additives that may be present in the formulation include antifoaming agents, foam inhibitors, corrosion inhibitors, metal deactivators, pour point inhibitors, antioxidants, and various well known additives.

Also within the scope of the present invention is the complete preparation of a lubricating oil containing a dispersible effective amount of a long chain aliphatic hydrocarbyl amine additive. Included in the fully formulated composition are;

1. Alkenyl succinic acid imide,

2. Dihydrocarbyl dithiophosphoric acid,

3. Adult alkali or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof,

4. Neutral or overbased alkaline or alkaline earth metal alkalized phenates and mixtures thereof,

5. Viscosity Index (VI) improver

The presence of alkenyl succinic acid acts as a dispersant and prevents precipitation formation during engine operation. Alkenyl succinic acid is known in the art. Alkenyl succinic acid is a reaction product of a polyolefin polymer substituted succinic anhydride and an amine, preferably a polyalkylene polyamine. The polyolefin polymer-substituted succinic anhydride is obtained by the reaction of a polyolefin polymer or derivative thereof with maleic anhydride. The thus obtained succinic anhydride is reacted with an amine compound. The preparation of alkenyl succinimide has been described many times in the art. See, for example, U.S. Patent Nos. 3,390,082; 3,219,666; And 3,172,892. This disclosure is incorporated herein by reference. Reduction of the alkenyl substituted succinic anhydride gives the corresponding alkyl derivative. Alkyl succinimide tends to be included in the scope of the alkenyl succinic acid imide term. The product consisting predominantly of mono-naphth-succinimide can be prepared by controlling the molar ratio of the reactants. Thus, for example, reacting 1 mole of an amine with 1 mole of alkenyl or alkyl substituted succinic anhydride will result in a predominantly mono-succinic acid imide product. When two moles of succinic anhydride are reacted per mole of polyamine, bis-succinic acid-imide is produced. When the alkenyl succinic acid imide is a polyisobutene-substituted succinic anhydride of polyalkylene polyamine, particularly good results are obtained as the lubricating oil composition of the present invention.

Polyisobutene obtained by polymerization of polyisobutene-substituted succinic anhydride with isobutene can vary widely in its composition. The average number of carbon atoms may range from 30 or less to 250 or more, such that the average number of carbon atoms is about 400 or less to about 3,000 or more. Preferably, the number of polyisobutene molecular weight average carbon atoms is in the range of about 50 to 100 and the polyisobutene has an average molecular weight of about 600 to about 1500. More preferably, the number of average carbon atoms per polyisobutene molecule ranges from about 60 to about 90 and the number average molecular weight ranges from about 800 to about 2500. Polyisobutene is reacted with maleic anhydride according to well known processes to obtain polyisobutene-substituted succinic anhydride.

In the preparation of the alkenyl succinimide, the substituted succinic anhydride is reacted with the polyalkylene polyamine to give the corresponding succinic acid imide. Each alkylene group of the polyalkylene polyamine usually has from 2 to about 89 carbon atoms. The alkylene groups usually have from 2 to about 8 carbon atoms. The number of alkylene groups may range up to about 8. Examples of the alkylene group include ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene and the like. The number of amino groups is generally not necessary, but is greater than the number of alkylene groups present in the amine. That is, when the polyalkylene polyamine contains three alkylene groups, it will typically contain four amino groups. The number of amino groups may range up to about 9. Preferably, the alkylene group contains from about 2 to 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups up to 1. Preferably, the polyalkylene polyamine contains 3 to 5 amine groups. Specific examples of polyalkylene polyamines are included in ethylenediamine, diethylenetriamine, triethylenepentamine, trimethylene diamine, pentaethylene-hexamine, di- (trimethylene) triamine, tri (hexamethylene) .

Other amines suitable for preparing alkenyl succinic acid imides useful in the present invention include cyclic amines such as the piperazine, morpholine and dipiperazines results. Preferred alkenyl succinic acid imides used in the compositions of the present invention have the general formula:

In the above formula

(a) R ₂ refers to an alkenyl group, preferably a sufficiently saturated hydrocarbon prepared by cascading an aliphatic monoolefin. Preferably R < _{1 >} is prepared in isobutane and has a number of average carbon atoms and an average molecular weight number as described above.

(b) an alkylene group refers to a generally hydrocarbyl group containing from about 2 to about 4 carbon atoms, as mentioned above, containing up to 2 to about 8 carbon atoms.

(c) A refers to a hydrocarbyl group, an amine-substituted hydrocarbyl group, or hydrogen. Hydrocarbyl groups and amine-substituted hydrocarbyl groups are generally alkyl and amino-substituted-alkyl analogs of the alkylene groups described above. Preferably A is hydrogen.

(d) n is an integer from 1 to about 8, preferably from about 3 to about 5.

Also included in the term alkenyl succinic acid imide is the modified succinic acid imide disclosed in U.S. Patent No. 4,612,132, which is incorporated herein by reference.

The alkenyl succinic acid imide is present in the lubricating oil composition of the present invention in an effective amount and acts as a dispersant to prevent settling of contaminants formed in the oil during engine operation. The amount of alkenyl succinimide may range from about 1% to about 20% by weight of the total lubricating oil composition. Preferably, the amount of alkenyl succinic acid imide present in the lubricating oil composition of the present invention is in the range of from about 1% to about 10% by weight of the total composition.

Alkali or alkaline earth metal hydrocarbyl sulfonates may be one of the synthetically alkylated aromatic sulfonates in petroleum sulfonates, or aliphatic sulfonates, such as those obtained from polyisobutylene. One of the more important functions of sulfonates is to act as a detergent or dispersant. Such sulfonates are known in the art. The hydrocarbyl group must have a sufficient number of carbon atoms to be an oil soluble sulfonate. Preferably, the hydrocarbyl moiety has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkylaromatic. The best to use is the aromatic component calcium, magnesium or barium sulfonate.

Some sulfonates are typically prepared by sulfonating a petroleum fraction having an aromatic group, typically a mono-di-alkylbenzene group, and then forming a metal salt of the sulfonate material. Another raw material used to prepare these sulfonates includes polyisobutenyl groups prepared by polymerizing synthetic allylated benzene and aliphatic hydrocarbons, such as isobutane, prepared by polymerizing mono- or di-olefins. Metal salts are made directly or by metallization using known methods.

Sulfonates may be either overbased with bases of up to about 400 or more, or neutral. Carbon dioxide, calcium hydroxide, or calcium oxide are the most commonly used materials to make basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates may also be used. Sulfonates are usually used to obtain from 6.3% to 10% of the total composition. Preferably, the neutral sulfonate is present in the total composition at 0.4% to 5% by weight and the overbased sulfonate is present in the total composition at 0.3% to 3% by weight.

The polycarboxylates for use in the present invention are the usual products of these which are alkaline or alkaline earth metal salts of alkalized phenols. One of the pre-carbonate functions is to act as a detergent and dispersant. In particular, it prevents precipitation of contaminants formed during high-temperature operation of the engine. The phenol may be mono or polyalkarylated.

The alkyl portion of the alkyl phenol is present to impart oil solubility to the phenolic acid. The alkyl moiety can be obtained by naturally occurring sources or by synthesis. Natural sources include petroleum hydrocarbons such as white oil and wax. What is obtained from petroleum is a mixture of hydrocarbyl groups with different hydrocarbon constituents, and its specific composition depends on the special oil feedstock used as starting material. Suitable synthetic sources include alkene and alkane derivatives that are capable of various commercial subscriptions to obtain alkylphenols upon reaction with phenol. Suitable groups obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, tricontyl, and the like. Another suitable source for the synthesis of alkyl groups is polypropylene, polybutylene, polyisobutylene, and the like.

The alkyl group can be saturated or unsaturated, which is linear or branched (branched chain) (preferably containing up to two olefinic unsaturation sites if unsaturated and generally containing about one olefinic unsaturation site). Alkyl groups generally contain from 4 to 30 carbon atoms. Generally, when phenol is substituted with monoalkyl, the alkyl group must contain at least 8 carbon atoms. The carbonate can also be sulphated if necessary.

It may be neutral or overbased, and if overbased, it may have a base number of 200 to 300 or more. Mixtures of neutral and overbased gypsum carbonate may be used.

The calcium carbonate is usually present in the oil in an amount of from 0.2% to 9% by weight of the total composition, from 0.2% to 27% by weight, and the overbased calcium carbonate is present in the entire composition in an amount of from 0.2 to 13% by weight. Most preferably, the overbased gypsum carbonate is present in the total composition in an amount of from 0.2% to 5% by weight. Preferred metals are calcium, magnesium, strontium or barium.

The vulcanized alkanitetallic alkyl-calcium carbonate is preferred. These salts are obtained by a variety of processes such as the treatment of the neutral and product of sulfur alkaline earth metal bases and alkyl phenols. Conveniently, the elemental sulfur is added to the neutralization product and reacted at a high temperature to obtain a vulcanized alkaline earth metal chelate carbonate.

When more alkaline earth metal base is added during the neutralization reaction than was needed to neutralize the phenol, a basic, vulcanized alkaline earth metal alkyl ammonium carbonate salt is obtained. For example, the process of U.S. Patent No. 2,680,096 to Walk et al can be referred to. The additional basicity can be obtained by adding carbon dioxide to the basic vulcanized alkaline earth metal alkylketocarbonate. Excess alkaline earth metal base may be added in succession to the vulcanization step, but conveniently added at the same time when the alkaline earth metal base is added to neutralize the phenol.

Carbon dioxide, calcium hydroxide and calcium oxide are the most commonly used materials to obtain basic or overbased gypsum. The pseudo-vulcanized alkaline earth metal alkylketate, obtained by the addition of carbon dioxide, is disclosed in U.S. Patent No. 3,178,368 to Hannnett.

Group II metal salts of dihydrocarbyl dithiophosphates exhibit abrasive antioxidant and thermal stability. Group II metal salts of phosphorodithioic acids have been described previously. See, for example, U.S. Pat. No. 3,390,050, columns 6 and 7, wherein these compounds and their preparation are generally described. Suitably, Group II metal salts of dihydrocarbyldithiophosphates useful in the lubricating oil composition of the present invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl groups and may be the same or different and may be aromatic, have. A preferred hydrocarbyl group is an alkyl group containing from 4 to 8 carbon atoms and is representative of butyl, isobutyl, sec-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. Suitable metals for forming these salts include barium, calcium, strontium, zinc and cadmium, with zinc being preferred.

Preferably, the Group II metal salt of dihydrocarbyldithiophosphate has the general formula:

In this formula,

(e) R ₃ and R ₄ each independently represent a hydrocarbyl group as described above;

(f) M ₁ represents a Group II metal cation as described above.

The dithiophosphate is present in the lubricating oil composition of the present invention in an effective amount to inhibit wear and oxidation of the lubricating oil. The amount is in the range of from about 0.1 to about 4% by weight in the total composition, and is preferably present in an amount such that the salt has a range of from about 0.2 to about 2.5% wax in the total lubricating oil composition. The final lubricating oil composition will usually contain from 0.025 to 0.25% by weight of phosphorus and preferably from 0.05 to 0.15% by weight.

Viscosity Index (VI) improvers are non - dispersants or dispersant VI improvers. Non-dispersant VI improvers are typically hydrocarbyl polymers including copolymers or terpolymers. Typically, the hydrocarbyl copolymers are copolymers of ethylene < RTI ID = 0.0 > Such non-dispersant VI improvers are described in U.S. Patent Nos. 2,700,633, which are incorporated herein by reference to provide knowledge of non-dispersant VI improvers; 2,726,231; 2,792,288; 2,933,480; 3,000,866; 3,063,973; And 3,093,621.

Dispersant VI improvers can be prepared by functionalizing the non-dispersant VI improvers. For example, the non-dispersible hydrocarbyl copolymer and the terpolymer VI modifier can be functionalized to produce an aminated and oxidized VI modifier having an average molecular weight number of 1500 to 20,000 with dispersibility. Such functionalized dispersant VI improvers are described in U.S. Patent No. 3,864,268, which is incorporated herein by reference in order to provide knowledge of VI improvers in its dispersion. 3,769,216; 3,326,804; And 3,316,177.

Other dispersant VI improvers are included as amine-bonded acrylic polymers and copolymers wherein one monomer contains at least one amino group. Typical compositions are described in British Patent No. 1,488,382; U.S. Patent Nos. 489,794 and 4,025,452, which are incorporated herein by reference for their knowledge of the dispersant VI improvers.

Non-dispersant and dispersant VI improvers are generally used in the lubricating oil composition at 5 to 20% by weight.

The following examples are provided to illustrate the invention in particular. These examples and illustrations are not to be construed as limiting the invention in any way.

[Example 1]

(Preparation of polyisobutyl-24 alcohol)

50 grams (0.0525 mole) of polyisobutene-24 (average molecular weight of about 950) dissolved in 200 ml of tetrahydrofuran (THF) was added to a dry, 1 -sun, round-bottomed flask equipped with a mechanical stirrer, ) Was added. The reaction vessel was cooled to 0 占 폚 and protected from moisture using a nitrogen atmosphere. Then it was added dropwise over a BH ₃ / THF solution of 53ml of 1M to about 25 minutes. The mixture was then warmed to room temperature and stirred for approximately 3 hours.

At that point, 10 ml of water was added dropwise to the mixture in a careful manner to avoid excessive bubbling. When the addition of water was completed, the vessel was cooled again to 0 ° C, treated with 18 ml of 3 M aqueous sodium hydroxide solution and then treated with 15 ml of 30% hydrogen peroxide. The reaction mixture was then heated to 50 < 0 > C with stirring for 2½ hours. Further, 25 ml portions of a 3M aqueous solution of sodium hydroxide were added and further stirring was continued for 0.5 hour.

After cooling, the reaction mixture was extracted three times with 500 ml of hexane. Collect the organic phases and wash twice with water (each about 500 ml); Washed once with saline (approximately 300 ml); Then, it was dried, filtered, and volatized to obtain 45.2 g of a product polyisobutyl alcohol [IR: OH-3460 cm ^-1 ; Hydroxy no. 56]. The product was used in Example 2 without further purification.

[Example 2]

(Preparation of polyisobutyl-24 alkyl chloride)

To a 500 ml round bottom flask equipped with a mechanical stirrer, condenser and heating mantle and sealed in water (nitrogen atmosphere), 53 g (0.05 ml) of polyisobutyl-24 alcohol (prepared according to the procedure outlined in Example 1) ) And 65 xylene was cited. To the flask, 6.1 g (124 M%) of epichlorohydrin was added in portions with 0.5 ml (0.557 g) of ethylbenzene boron trifluoride. The reaction mixture was then heated to 65 DEG C with stirring for about 3 hours. The temperature of the reaction mixture was then increased to 80 DEG C and maintained at that temperature for another 2 hours.

After removing the heat source, the reaction mixture was cooled with 2 g of sodium bicarbonate, stirred for 15 minutes, and then purified overnight. The solids were removed by suction filtration. The filtrate containing the above-mentioned product was diluted to 150 ml with xylene and used in the process described in Example 3 without further purification and / or separation.

[Example 3]

(Preparation of polybutyl-24 aminoether)

Necked flask equipped with a mechanical stirrer, condenser and heating mantle and isolated from water (in N ₂ atmosphere) in a 500 ml three-necked flask was charged with 150 ml of an alkyl chloride (in xylene) mixture (the product of the example) and 112 ml (100 g) ≪ / RTI > The stirred reaction mixture was heated to 120 < 0 > C and stirred at that temperature for 4 hours. The xylene excess ethylenediamine was then removed by vacuum distillation. The residue was diluted with hexane and washed three times with a strong aqueous base (NaOH) solution, washed successively with brine, dried over magnesium sulfate, filtered and evaporated to give a clear amber viscous oil (AV = 93) A product is obtained.

[Example 4]

(Preparation of polyisobutyl-32 alcohol)

Manufactured according to the process described in Example 1 with polypolyisobutene-32 of polyisobutyl alcohol (average molecular weight of about 1300), but using the following ratio of materials; 555 g of polyisobutene-32 was dissolved in 2 L of tetrahydrofuran (THF) and then treated with 400 ml of a 1 M solution of BH ₃ / THF. The reaction mixture is cooled with 80 ml of water, then it is cooled with 135 ml of 3 M aqueous sodium hydroxide solution and again treated with 55 ml of 30% hydrogen peroxide. After separation, 542 g of the above-mentioned product are obtained as a dark fog-like liquid with a hydroxyl number of 48.0.

[Example 5]

(Preparation of polyisobutyl-32 alkyl chloride)

The alkyl chloride as described above was prepared from the polyisobutyl-32 alcohol prepared by Example 4 according to the process described in Example 2 using the following amounts of the following materials: : By dissolving a polyisobutylene -32 alcohol 53g in 65ml of xylene, treated with Tel cargo on epichlorohydrin and 0.5ml of BF ₃ to obtain the above-mentioned alkyl chloride of 4.25ml of 57g. After dilution with 50 ml xylene, alkyl chloride can be used to prepare the corresponding aminoethers.

[Example 6]

(Preparation of polyisobutyl-32 aminoether)

The polyisobutyl-32 alkylamine is prepared from its corresponding alkyl chloride (prepared according to the process described in Example 5) using the following proportions of the following materials: A solution of 57 g of polyisobutyl-32-alkyl chloride in 50 ml of xylene was treated with 100 g of ethylenediamine to obtain 58 g of the above aminoether as a dark yellowish brown oil (AV = 50.8).

[Example A]

The stability of the fuel additives prepared according to the process outlined in Examples 1 to 3 was measured by thermal hydrometer analysis (TGA). The TGA process using a DuPont 951 TGA machine is paired with a microcomputer for data analysis. A sample of the fuel additive (about 25 mg) was heated at 200 ° C by isothermal flow while flowing air at 100 cm ³ / min. The weight of the sample was detected as a function of time. The increased weight loss is believed to be in the first order process. The kinetic data, the proportional constant and the half-life, were easily measured from the accumulated TGA data. The half life measured by this process represents the time taken for half of the additive to decompose. The half-life data for the fuel additive is related to the possibility that the additive will affect the ORI. The lower half-life refers to the more easily degradable products, one of which does not seem to accumulate and form precipitates in the combustion chamber. The high half-life, approaching 900 minutes, refers to the ORI problem in engine operation. The obtained half-life results are shown in Table 1 below.

Claims (37)

Long chain aliphatic hydrocarbyl amine additive of the general formula: R-X-Am Wherein R is an aliphatic hydrocarbyl component having a chain length of at least 50 carbon atoms; Am is an amine component having at least one basic nitrogen atom; X is -OCH ₂ CHOHCH ₂ - and Or a mixture thereof. The additive according to claim 1, wherein at least one basic nitrogen source among the amine components is present as a primary or secondary amine group. The additive of claim 1, wherein the amine component is derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms in a carbon: nitrogen ratio of between 1: 1 and 10: 1. 4. The method of claim 3 wherein the polyamine is selected from the group consisting of (A) hydrogen, (B) a hydrocarbyl group of from 1 to about 10 carbon atoms, (C) an acyl group of from 2 to about 10 carbon atoms, (D) And (C) monoketo, monohydroxy, mononitro, monocyano, polyamines substituted by substituents selected from lower alkyl and lower alkoxy derivatives. 4. The additive of claim 3, wherein the polyamine is a polyalkylene polyamine wherein the alkylene group contains 2 to 6 carbon atoms and the polyamine is 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms. The method according to claim 5, wherein the polyalkylene polyamine is selected from the group consisting of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine and 1,3-diaminopropane. ≪ / RTI > 7. The additive of claim 6, wherein the aliphatic hydrocarbyl component comprises a polymeric hydrocarbon having an average molecular weight of from about 700 to about 3,000. 8. The additive of claim 7, wherein the aliphatic hydrocarbyl component comprises polyisobutylene having an average molecular weight of about 900 to 2,000. The additive of claim 8, wherein the polyamine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or 1,3-diaminopropane. 9. The additive of claim 8, wherein the aliphatic hydrocarbyl component comprises polyisobutylene having an average molecular weight of from about 950 to about 1,600. The additive according to claim 10, wherein the polyamine is ethylenediamine or diethylenetriamine. 12. The additive of claim 11, wherein the aliphatic hydrocarbyl component has an average molecular weight of about 950. 12. The additive of claim 11, wherein the aliphatic hydrocarbyl component has an average molecular weight of about 1,300. The method of claim 1 wherein, X is mainly -OCH ₂ CHOHCH ₂ - additives. 15. The additive of claim 14, wherein R is polyisobutylene or polypropylene. 16. The additive of claim 15, wherein Am is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or 1,3-diaminopropane. 17. The additive of claim 16, wherein R is polyisobutylene having an average molecular weight of from about 900 to about 2,000. 18. The additive of claim 17, wherein Am is ethylenediamine or diethylenetriamine. 19. The additive of claim 18, wherein R is polyisobutyl-24 or polyisobutyl-32. The following general formula RO-CH ₂ CHOHCH ₂ -NH (R ₁ NH) Or a mixture thereof, wherein R is an aliphatic hydrocarbyl component having an average chain length of at least 50 carbon atoms; R ₁ is alkylene of 2 to 6 carbon atoms and p is an integer of 1 to 6. 21. The additive of claim 20, wherein R is polypropyl, polybutyl or polyisobutyl. 22. The additive of claim 21, wherein R is polyisobutylene having an average molecular weight of from about 700 to about 3,000. 23. The additive of claim 22, wherein R < _{1 >} is ethylene. 24. The additive of claim 23, wherein p is one or two. 25. The additive of claim 24, wherein R is polyisobutyl-24 or polyisobutyl-32. 1. A fuel composition comprising hydrocarbon from boiling in gasoline or diesel range and from about 30 to about 5,000 ppm of an additive according to claim 1. A fuel composition comprising hydrocarbons boiling in the gasoline or diesel range and from about 30 to about 5,000 ppm of an additive according to claim 20. 25. A fuel composition comprising hydrocarbon from boiling in the range of gasoline or diesel and from about 30 to about 5,000 ppm of an additive according to claim 25. A fuel concentrate containing an inert stable oleophilic organic solvent boiling in the range of 65.5 DEG C to 204.5 DEG C and from about 5 to about 50 wt.% Of an additive according to claim 1. A fuel concentrate containing an inert stable oleophilic organic solvent boiling in the range of 65.5 DEG C to 204.5 DEG C and from about 5 to about 50 wt.% Of the additive according to claim 24. A fuel concentrate containing an inert stable oleophilic organic solvent boiling in the range of 65.5 DEG C to 204.5 DEG C and about 5 to about 50 wt.% Of the additive according to claim 36. A lubricating oil composition comprising an oil of lubricating viscosity and 0.2 to 10% by weight of an additive according to claim 1. A lubricating oil composition comprising an oil of lubricating viscosity and 0.2 to 10% by weight of an additive according to claim 20. A lubricating oil composition comprising an oil of lubricating viscosity and 0.2 to 10% by weight of an additive according to claim 23. About 90 to about 50 percent by weight of an oil of lubricating viscosity and about 10 to about 50 percent by weight of an additive according to claim 1. From about 90 to about 50 percent by weight of an oil of lubricating viscosity and from about 10 to about 50 percent by weight of an additive according to claim 20. From about 90 to about 50 percent by weight of an oil of lubricating viscosity and from about 10 to about 50 percent by weight of an additive according to claim 25.